Ethyl 2-amino-4-(4-fluoro­phen­yl)-4H-benzo[h]chromene-3-carboxyl­ate

The title compound, C₂₂H₁₈FNO₃, was synthesized by the reaction of 1-naphthol with ethyl cyano­caetate and 4-fluoro­benzaldehyde in ethanol under microwave irradiation. The pyran ring adopts a flattened envelope conformation. The mol­ecular conformation and the crystal structure are stabilized by N—H...O hydrogen bonds.

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.004 Å
• R factor = 0.057
• wR factor = 0.181
• Data-to-parameter ratio = 14.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical .          ?
PLAT720_ALERT_4_C Number of Unusual/Non-Standard Label(s) ........          2

Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   2 ALERT level C = Check and explain
   2 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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Computing details

Data collection: CAD-4 Software (Enraf–Nonius, 1989); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Siemens, 1996); software used to prepare material for publication: SHELXTL.

Ethyl 2-amino-4-(4-fluorophenyl)-4H-benzo[h]chromene-3-carboxylate

Crystal data

C22H18FNO3	F(000) = 760
Mr = 363.37	Dx = 1.341 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 12.634 (3) Å	θ = 10–13°
b = 16.037 (3) Å	µ = 0.10 mm^−1
c = 8.9890 (18) Å	T = 293 K
β = 98.77 (3)°	Block, light brown
V = 1800.0 (7) Å^3	0.40 × 0.30 × 0.30 mm
Z = 4

Data collection

Enraf-Nonius CAD-4 diffractometer	2038 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.019
Graphite monochromator	θmax = 26.0°, θmin = 1.6°
ω/2θ scans	h = −15→15
Absorption correction: ψ scan (North et al., 1968)	k = −19→0
Tmin = 0.967, Tmax = 0.972	l = 0→11
3755 measured reflections	3 standard reflections every 200 reflections
3519 independent reflections	intensity decay: none

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.057	H-atom parameters constrained
wR(F^2) = 0.181	w = 1/[σ^2(Fo^2) + (0.0891P)^2 + 0.5068P] where P = (Fo^2 + 2Fc^2)/3
S = 0.99	(Δ/σ)max < 0.001
3519 reflections	Δρmax = 0.20 e Å^−3
247 parameters	Δρmin = −0.19 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.013 (3)

Special details

Experimental. ¹H NMR (CDCl₃): δ 8.22 (d, 1H), 7.76 (d, 1H), 7.55 (d, 1H), 7.48 (m, 2H), 7.11 (d, 1H), 6.48 (d, 2H), 5.05 (s, 1H), 4.09 (s, 2H), 1.18 (s, 3H).

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
F	0.20313 (16)	1.28307 (12)	0.3511 (2)	0.0899 (6)
O1	0.13381 (14)	0.92121 (12)	0.54825 (18)	0.0589 (5)
O2	0.01637 (14)	0.83381 (12)	0.41532 (19)	0.0579 (5)
O3	0.19701 (13)	0.85127 (12)	0.06117 (18)	0.0553 (5)
N	0.04402 (18)	0.80907 (16)	0.1266 (3)	0.0650 (7)
H0A	0.0313	0.7896	0.0365	0.113 (14)*
H0B	−0.0025	0.8029	0.1864	0.073 (10)*
C1	0.1104 (3)	0.9912 (2)	0.7735 (3)	0.0774 (10)
H1A	0.0675	0.9951	0.8527	0.116*
H1B	0.1098	1.0438	0.7223	0.116*
H1C	0.1826	0.9771	0.8156	0.116*
C2	0.0657 (2)	0.9251 (2)	0.6644 (3)	0.0661 (8)
H2A	0.0652	0.8717	0.7150	0.079*
H2B	−0.0072	0.9388	0.6204	0.079*
C3	0.0978 (2)	0.87601 (17)	0.4246 (3)	0.0475 (6)
C4	0.16660 (19)	0.88480 (16)	0.3109 (3)	0.0458 (6)
C5	0.13549 (19)	0.84867 (16)	0.1735 (3)	0.0469 (6)
C6	0.30286 (19)	0.87672 (16)	0.0981 (3)	0.0474 (6)
C7	0.3675 (2)	0.86008 (16)	−0.0161 (3)	0.0506 (7)
C8	0.3265 (3)	0.82576 (17)	−0.1574 (3)	0.0632 (8)
H8A	0.2545	0.8114	−0.1796	0.076*
C9	0.3935 (3)	0.81357 (19)	−0.2623 (4)	0.0763 (10)
H9A	0.3661	0.7926	−0.3568	0.092*
C10	0.5017 (3)	0.8322 (2)	−0.2285 (5)	0.0890 (11)
H10A	0.5464	0.8226	−0.2999	0.107*
C11	0.5430 (3)	0.8643 (2)	−0.0922 (5)	0.0839 (11)
H11A	0.6159	0.8758	−0.0711	0.101*
C12	0.4774 (2)	0.88044 (19)	0.0179 (4)	0.0641 (8)
C13	0.5174 (2)	0.9161 (2)	0.1593 (4)	0.0779 (10)
H13A	0.5900	0.9284	0.1827	0.093*
C14	0.4512 (2)	0.9326 (2)	0.2609 (3)	0.0694 (9)
H14A	0.4791	0.9570	0.3524	0.083*
C15	0.34175 (19)	0.91355 (17)	0.2312 (3)	0.0486 (7)
C16	0.26836 (18)	0.93544 (16)	0.3437 (3)	0.0461 (6)
H16A	0.3047	0.9193	0.4437	0.055*
C17	0.24897 (18)	1.02926 (16)	0.3457 (3)	0.0449 (6)
C18	0.2834 (2)	1.07582 (19)	0.4740 (3)	0.0565 (7)
H18A	0.3175	1.0489	0.5598	0.068*
C19	0.2684 (2)	1.1613 (2)	0.4776 (3)	0.0674 (8)
H19A	0.2918	1.1920	0.5641	0.081*
C20	0.2183 (2)	1.19882 (19)	0.3499 (3)	0.0602 (8)
C21	0.1817 (2)	1.15617 (19)	0.2206 (3)	0.0588 (7)
H21A	0.1468	1.1837	0.1360	0.071*
C22	0.1980 (2)	1.07103 (18)	0.2195 (3)	0.0510 (7)
H22A	0.1743	1.0410	0.1322	0.061*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
F	0.1022 (14)	0.0661 (12)	0.1045 (16)	0.0131 (10)	0.0256 (12)	−0.0075 (11)
O1	0.0620 (11)	0.0817 (14)	0.0367 (10)	−0.0052 (10)	0.0192 (8)	−0.0033 (9)
O2	0.0567 (11)	0.0699 (13)	0.0501 (11)	−0.0061 (10)	0.0181 (9)	0.0083 (10)
O3	0.0514 (10)	0.0772 (13)	0.0399 (10)	−0.0065 (9)	0.0157 (8)	−0.0084 (9)
N	0.0573 (14)	0.0851 (18)	0.0564 (16)	−0.0166 (13)	0.0207 (12)	−0.0200 (14)
C1	0.096 (2)	0.093 (2)	0.0468 (17)	0.0183 (19)	0.0217 (16)	−0.0001 (17)
C2	0.0729 (19)	0.092 (2)	0.0388 (14)	0.0082 (16)	0.0246 (13)	0.0026 (15)
C3	0.0500 (15)	0.0555 (16)	0.0381 (14)	0.0044 (13)	0.0100 (12)	0.0054 (12)
C4	0.0484 (14)	0.0549 (16)	0.0359 (13)	0.0017 (12)	0.0127 (11)	0.0022 (12)
C5	0.0465 (14)	0.0537 (15)	0.0437 (14)	0.0005 (12)	0.0166 (12)	0.0007 (12)
C6	0.0486 (14)	0.0523 (15)	0.0440 (14)	0.0060 (12)	0.0157 (12)	0.0030 (12)
C7	0.0638 (17)	0.0468 (16)	0.0452 (15)	0.0071 (12)	0.0212 (13)	0.0050 (12)
C8	0.082 (2)	0.0583 (18)	0.0558 (17)	0.0011 (15)	0.0306 (15)	−0.0034 (15)
C9	0.116 (3)	0.060 (2)	0.064 (2)	0.0026 (18)	0.0477 (19)	−0.0085 (16)
C10	0.108 (3)	0.082 (2)	0.094 (3)	0.006 (2)	0.072 (2)	−0.002 (2)
C11	0.075 (2)	0.091 (3)	0.098 (3)	0.0079 (19)	0.052 (2)	0.001 (2)
C12	0.0556 (17)	0.071 (2)	0.072 (2)	0.0069 (15)	0.0305 (15)	0.0056 (17)
C13	0.0473 (17)	0.113 (3)	0.076 (2)	−0.0037 (17)	0.0165 (16)	−0.007 (2)
C14	0.0530 (17)	0.097 (2)	0.0586 (18)	0.0001 (16)	0.0111 (14)	−0.0096 (17)
C15	0.0453 (14)	0.0592 (17)	0.0428 (14)	0.0035 (12)	0.0119 (11)	0.0035 (13)
C16	0.0455 (14)	0.0628 (17)	0.0310 (12)	0.0023 (12)	0.0089 (10)	0.0006 (12)
C17	0.0407 (13)	0.0614 (17)	0.0342 (13)	−0.0035 (12)	0.0106 (10)	−0.0035 (12)
C18	0.0560 (16)	0.074 (2)	0.0390 (14)	0.0037 (14)	0.0047 (12)	−0.0064 (14)
C19	0.073 (2)	0.075 (2)	0.0557 (18)	0.0019 (17)	0.0125 (15)	−0.0194 (17)
C20	0.0593 (17)	0.059 (2)	0.066 (2)	0.0022 (14)	0.0236 (15)	−0.0003 (16)
C21	0.0555 (16)	0.070 (2)	0.0522 (17)	0.0009 (14)	0.0123 (13)	0.0093 (15)
C22	0.0520 (15)	0.0640 (19)	0.0373 (14)	−0.0031 (13)	0.0077 (12)	0.0005 (13)

Geometric parameters (Å, º)

F—C20	1.365 (3)	C9—C10	1.387 (5)
O1—C3	1.347 (3)	C9—H9A	0.9300
O1—C2	1.452 (3)	C10—C11	1.358 (5)
O2—C3	1.223 (3)	C10—H10A	0.9300
O3—C5	1.366 (3)	C11—C12	1.409 (4)
O3—C6	1.389 (3)	C11—H11A	0.9300
N—C5	1.330 (3)	C12—C13	1.415 (4)
N—H0A	0.8600	C13—C14	1.355 (4)
N—H0B	0.8600	C13—H13A	0.9300
C1—C2	1.496 (4)	C14—C15	1.402 (4)
C1—H1A	0.9600	C14—H14A	0.9300
C1—H1B	0.9600	C15—C16	1.513 (3)
C1—H1C	0.9600	C16—C17	1.525 (3)
C2—H2A	0.9700	C16—H16A	0.9800
C2—H2B	0.9700	C17—C18	1.387 (3)
C3—C4	1.446 (3)	C17—C22	1.389 (3)
C4—C5	1.367 (3)	C18—C19	1.384 (4)
C4—C16	1.511 (3)	C18—H18A	0.9300
C6—C15	1.358 (3)	C19—C20	1.364 (4)
C6—C7	1.431 (3)	C19—H19A	0.9300
C7—C8	1.409 (4)	C20—C21	1.367 (4)
C7—C12	1.414 (4)	C21—C22	1.381 (4)
C8—C9	1.374 (4)	C21—H21A	0.9300
C8—H8A	0.9300	C22—H22A	0.9300
C3—O1—C2	117.0 (2)	C9—C10—H10A	119.7
C5—O3—C6	117.91 (19)	C10—C11—C12	121.2 (3)
C5—N—H0A	120.0	C10—C11—H11A	119.4
C5—N—H0B	120.0	C12—C11—H11A	119.4
H0A—N—H0B	120.0	C11—C12—C7	118.0 (3)
C2—C1—H1A	109.5	C11—C12—C13	122.5 (3)
C2—C1—H1B	109.5	C7—C12—C13	119.5 (2)
H1A—C1—H1B	109.5	C14—C13—C12	120.8 (3)
C2—C1—H1C	109.5	C14—C13—H13A	119.6
H1A—C1—H1C	109.5	C12—C13—H13A	119.6
H1B—C1—H1C	109.5	C13—C14—C15	121.4 (3)
O1—C2—C1	107.2 (2)	C13—C14—H14A	119.3
O1—C2—H2A	110.3	C15—C14—H14A	119.3
C1—C2—H2A	110.3	C6—C15—C14	118.5 (2)
O1—C2—H2B	110.3	C6—C15—C16	120.9 (2)
C1—C2—H2B	110.3	C14—C15—C16	120.6 (2)
H2A—C2—H2B	108.5	C4—C16—C15	109.6 (2)
O2—C3—O1	121.9 (2)	C4—C16—C17	113.5 (2)
O2—C3—C4	126.6 (2)	C15—C16—C17	110.7 (2)
O1—C3—C4	111.5 (2)	C4—C16—H16A	107.6
C5—C4—C3	118.4 (2)	C15—C16—H16A	107.6
C5—C4—C16	121.5 (2)	C17—C16—H16A	107.6
C3—C4—C16	120.0 (2)	C18—C17—C22	117.9 (3)
N—C5—O3	110.2 (2)	C18—C17—C16	120.7 (2)
N—C5—C4	127.3 (2)	C22—C17—C16	121.4 (2)
O3—C5—C4	122.5 (2)	C19—C18—C17	121.7 (3)
C15—C6—O3	123.0 (2)	C19—C18—H18A	119.1
C15—C6—C7	123.0 (2)	C17—C18—H18A	119.1
O3—C6—C7	114.1 (2)	C20—C19—C18	117.7 (3)
C8—C7—C12	119.9 (2)	C20—C19—H19A	121.1
C8—C7—C6	123.3 (2)	C18—C19—H19A	121.1
C12—C7—C6	116.8 (2)	C19—C20—F	118.6 (3)
C9—C8—C7	119.6 (3)	C19—C20—C21	123.2 (3)
C9—C8—H8A	120.2	F—C20—C21	118.2 (3)
C7—C8—H8A	120.2	C20—C21—C22	118.0 (3)
C8—C9—C10	120.6 (3)	C20—C21—H21A	121.0
C8—C9—H9A	119.7	C22—C21—H21A	121.0
C10—C9—H9A	119.7	C21—C22—C17	121.4 (3)
C11—C10—C9	120.6 (3)	C21—C22—H22A	119.3
C11—C10—H10A	119.7	C17—C22—H22A	119.3
C3—O1—C2—C1	−168.8 (2)	C7—C12—C13—C14	−1.4 (5)
C2—O1—C3—O2	−6.5 (4)	C12—C13—C14—C15	1.2 (5)
C2—O1—C3—C4	173.5 (2)	O3—C6—C15—C14	176.4 (2)
O2—C3—C4—C5	5.8 (4)	C7—C6—C15—C14	−3.1 (4)
O1—C3—C4—C5	−174.2 (2)	O3—C6—C15—C16	−5.0 (4)
O2—C3—C4—C16	−176.3 (2)	C7—C6—C15—C16	175.6 (2)
O1—C3—C4—C16	3.8 (3)	C13—C14—C15—C6	1.0 (5)
C6—O3—C5—N	−168.6 (2)	C13—C14—C15—C16	−177.6 (3)
C6—O3—C5—C4	13.1 (4)	C5—C4—C16—C15	−19.7 (3)
C3—C4—C5—N	4.2 (4)	C3—C4—C16—C15	162.3 (2)
C16—C4—C5—N	−173.7 (3)	C5—C4—C16—C17	104.5 (3)
C3—C4—C5—O3	−177.7 (2)	C3—C4—C16—C17	−73.4 (3)
C16—C4—C5—O3	4.3 (4)	C6—C15—C16—C4	19.9 (3)
C5—O3—C6—C15	−12.8 (4)	C14—C15—C16—C4	−161.5 (2)
C5—O3—C6—C7	166.7 (2)	C6—C15—C16—C17	−106.0 (3)
C15—C6—C7—C8	−176.7 (3)	C14—C15—C16—C17	72.6 (3)
O3—C6—C7—C8	3.8 (4)	C4—C16—C17—C18	120.3 (2)
C15—C6—C7—C12	2.8 (4)	C15—C16—C17—C18	−116.1 (2)
O3—C6—C7—C12	−176.7 (2)	C4—C16—C17—C22	−60.7 (3)
C12—C7—C8—C9	−1.1 (4)	C15—C16—C17—C22	63.0 (3)
C6—C7—C8—C9	178.4 (3)	C22—C17—C18—C19	−0.2 (4)
C7—C8—C9—C10	2.1 (5)	C16—C17—C18—C19	178.8 (2)
C8—C9—C10—C11	−1.2 (5)	C17—C18—C19—C20	0.0 (4)
C9—C10—C11—C12	−0.7 (6)	C18—C19—C20—F	−179.7 (2)
C10—C11—C12—C7	1.7 (5)	C18—C19—C20—C21	0.6 (4)
C10—C11—C12—C13	−178.1 (3)	C19—C20—C21—C22	−0.9 (4)
C8—C7—C12—C11	−0.8 (4)	F—C20—C21—C22	179.4 (2)
C6—C7—C12—C11	179.7 (3)	C20—C21—C22—C17	0.6 (4)
C8—C7—C12—C13	179.0 (3)	C18—C17—C22—C21	−0.1 (4)
C6—C7—C12—C13	−0.5 (4)	C16—C17—C22—C21	−179.1 (2)
C11—C12—C13—C14	178.4 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N—H0B···O2	0.86	2.09	2.700 (3)	127
N—H0A···O2^i	0.86	2.26	2.966 (3)	140

Symmetry code: (i) x, −y+3/2, z−1/2.